U.S. patent number 10,501,606 [Application Number 16/060,437] was granted by the patent office on 2019-12-10 for modified cellulose fibers and preparation method.
This patent grant is currently assigned to Technische Universitat Berlin. The grantee listed for this patent is Technische Universitat Berlin. Invention is credited to Niklas Ole Brandt, Thomas Kunz, Frank-Jurgen Methner.
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United States Patent |
10,501,606 |
Kunz , et al. |
December 10, 2019 |
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( Certificate of Correction ) ** |
Modified cellulose fibers and preparation method
Abstract
The invention relates to a method for the preparation of
modified cellulose fibers for artificial clarification of active
haze substances from liquids. In addition, the invention relates to
a modified cellulose fiber obtained by the method according to the
invention for artificial clarification of active haze substances
from a liquid, and to auxiliary filtering means containing one or
more of the modified cellulose fibers.
Inventors: |
Kunz; Thomas (Berlin,
DE), Brandt; Niklas Ole (Berlin, DE),
Methner; Frank-Jurgen (Bitburg, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Technische Universitat Berlin |
Berlin |
N/A |
DE |
|
|
Assignee: |
Technische Universitat Berlin
(Berlin, DE)
|
Family
ID: |
57590490 |
Appl.
No.: |
16/060,437 |
Filed: |
December 7, 2016 |
PCT
Filed: |
December 07, 2016 |
PCT No.: |
PCT/EP2016/080155 |
371(c)(1),(2),(4) Date: |
June 08, 2018 |
PCT
Pub. No.: |
WO2017/097864 |
PCT
Pub. Date: |
June 15, 2017 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20190002669 A1 |
Jan 3, 2019 |
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Foreign Application Priority Data
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Dec 8, 2015 [DE] |
|
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10 2015 121 383 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K
3/36 (20130101); B01D 39/18 (20130101); C08L
1/02 (20130101); C08L 2203/12 (20130101); B01D
2239/10 (20130101); C08L 3/02 (20130101); C08L
39/04 (20130101); C08L 2205/16 (20130101) |
Current International
Class: |
C08L
1/02 (20060101); C08K 3/36 (20060101); B01D
39/18 (20060101); C08L 3/02 (20060101); C08L
39/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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101445609 |
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Jun 2009 |
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CN |
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104312809 |
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Jan 2015 |
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CN |
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4110252 |
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Feb 1992 |
|
DE |
|
69124983 |
|
Oct 1997 |
|
DE |
|
102004962617 |
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Jul 2006 |
|
DE |
|
1333906 |
|
Aug 2003 |
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EP |
|
2280098 |
|
Feb 2011 |
|
EP |
|
55111842 |
|
Aug 1980 |
|
JP |
|
5840145 |
|
Mar 1983 |
|
JP |
|
WO-2011012424 |
|
Feb 2011 |
|
WO |
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2015036372 |
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Mar 2015 |
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WO |
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2015110694 |
|
Jul 2015 |
|
WO |
|
Other References
English-language machine translation of CN 101445609A (2009). cited
by examiner .
Chunyu Chang, et al., "Superabsorbent Hydrogels Based on Cellulose
for Smart Swelling and Controllable Delivery," 46 European Polymer
Journal 92-100 (2010). cited by examiner .
Braun, F. et al., "Large-Scale Study on Beer Filtration with
Combined Filter Aid Additions to Cellulose Fibers", Journal of the
Institute of Brewing, publication No. G-2011-0921-1107, 2011, p.
314-328. cited by applicant .
International Search Report and Written Opinion of the
International Searching Authority received in PCT/EP2016/080155,
dated Mar. 8, 2017 (11 pgs.). cited by applicant .
International Search Report received in PCT/EP2016/080155, dated
Mar. 8, 2017(4 pgs.). cited by applicant .
International Preliminary Report on Patentability received in
PCT/EP2016/080155, dated Jun. 14, 2018 (12 pgs.). cited by
applicant.
|
Primary Examiner: Hill; Nicholas E
Attorney, Agent or Firm: Guterman; Sonia K. Arun; Preeti T.
Armis Intellectual Property Law, LLC
Claims
The invention claimed is:
1. A method for producing modified cellulose fibers for artificial
clarification of turbidity-causing substances from beverages for
human consumption, the method comprising the following steps:
preparing a fiber mixture comprising 80-99.9 wt % cellulose fibers,
0.1-10 wt % sodium croscarmellose and 0-10 wt % of one or more
additives; swelling and adjusting the volume and pH of the fiber
mixture in a neutral to alkaline medium; heating the fiber mixture;
washing the cooked fiber mixture to obtain a moist mass of the
modified cellulose fibers; and, isolating the modified cellulose
fibers to obtain a resulting finished fibers mixture for treatment
for clarification of beverages for human consumption.
2. The method according to claim 1, wherein the fiber mixture for
production of modified cellulose fibers is homogenized.
3. The method according to claim 1, wherein the cellulose fibers
are selected from the group of fibers containing cellulose,
cellulose containing fibers, fibers from grains, from wood, from
bamboo, from wood chips, from wood wastes and mixtures of same, and
wherein the fibers have an average fiber length in the range of
<1 to 500 .mu.m.
4. The method according to claim 1, wherein the fiber mixture
according to step (a) comprises 92-99 wt % cellulose fibers, 1-8 wt
% sodium croscarmellose and 0-4 wt % of one or more additives.
5. The method according to claim 1, wherein the fiber mixture
according to step (a) is selected from a composition consisting of
90-99.9 wt % cellulose fibers, 0.1-5 wt % sodium croscarmellose and
0-5 wt % of one or more additives or from 90-99 wt % cellulose
fibers and 1-5 wt % sodium croscarmellose and 0-5 wt % of one or
more additives.
6. The method according to claim 1, wherein one or more additives
are selected from the group of additives consisting of pectin,
carrageenan, isinglass, hydrocolloids, starch, gallotannins, silica
sol, silica gel, polyvinylpyrrolidone and polyvinylpolypyrrolidone
as well as mixtures of same.
7. The method according to claim 1, wherein for workup of the fiber
mixture, the pH is adjusted with at least one acid and/or with at
least one base to a value between pH 6 and pH 13.
8. The method according to claim 1, further comprising after
washing, drying the moist mass to a residual water content of 2-10
wt % to obtain a dry mass.
9. A method for producing modified cellulose fibers for artificial
clarification of turbidity-causing substances from liquids, the
method comprising the following steps: preparing a fiber mixture
comprising 80-99.9 wt % cellulose fibers, 0.1-10 wt % sodium
croscarmellose and 0-10 wt % of one or more additives; swelling and
adjusting the volume and pH of the fiber mixture in a neutral to
alkaline medium; heating the fiber mixture; washing the cooked
fiber mixture to obtain a moist mass of the modified cellulose
fibers; and, isolating the modified cellulose fibers to obtain a
resulting finished fibers mixture, wherein the finished fiber
mixture is processed in an additional method step using the moist
mass to form filter aids and/or filter sheets.
10. The method according to claim 9 wherein the additional method
step comprises at least one process selected from layering,
tamping, absorbing, pressing, and pouring the moist mass of the
modified cellulose fibers into filter units.
11. The method according to claim 10 comprising preparing a filter
aid by inserting at least one of the filter units into at least one
of: deadend tube filters, deadend sheet filters, deadend disk
filters, deadend leaf filters and layered sheet filters.
12. The method according to claim 9 further comprising after
washing, drying the moist mass to a residual water content of 2-10
wt % to obtain a dry mass, wherein the dry mass finished fibers
mixture is processed using at least one selected from layering,
tamping, absorbing, and pressing the dry mass modified cellulose
fibers into dry mass filter units.
13. The method according to claim 12 further comprising preparing
dry mass filter aids by inserting at least one of the dry mass
filter units into at least one off; deadend tube filters, deadend
sheet filters, deadend disk filters, deadend leaf filters and
layered sheet filters.
Description
RELATED APPLICATIONS
This application is a national phase application and claims the
benefit of international application serial number
PCT/EP2015/080155 filed Dec. 7, 2016 which claims the benefit of
German application serial number 10 2015 121 383.4 filed Dec. 8,
2015, both of which are hereby incorporated herein by reference in
their entireties.
The invention relates to a method for producing modified cellulose
fibers for use in methods for artificial clarification of
turbidity-causing substances from liquids. Furthermore the
invention relates to the use of the modified cellulose fibers as a
filter aid for artificial clarification of turbidity-causing
substances from liquids.
The most important quality features of clear beverages such as
beer, wine, juices and other liquids, besides the taste, odor and
color, also include the physicochemical stability and the clarity.
To obtain sparkling clear beers and wines or juices, they must be
filtered.
In particular in the production of beer, a quantity of turbidity
substances such as yeast cells, hops resins or protein-tannin
compounds are still in suspension after aging is concluded. These
substances give the beer a milky and cloudy appearance. In addition
such turbidity-causing substances can also have a negative
influence on the taste and aroma of the beer.
Filtration, also known as artificial clarification, is therefore
the last step a beer must pass through after aging and before
bottling. Aging (natural clarification) already improves the
colloidal stability of beer through sedimentation of
turbidity-causing substances. In addition the stability of beer can
be improved by using stabilizers and an additional filtration
(artificial clarification). The most important reasons for
requiring filtration include: Removing turbidity substances such as
yeast cells, hops resins or protein tannin compounds; Additional
reduction of substances such as proteins or tannins that can form
renewed turbidity in filtered beer; Removing microorganisms such as
yeasts or bacteria; Clear appearance; Sensorial improvement.
Various filtration methods are known for obtaining a clear and
microbe-free beer. One popular method is to use deadend filtration
with diatomaceous earth or other filter aids, such as perlite,
cellulose and Crosspure.RTM.. It is also customary to use sheet
filters in the form of prepared filter layers (sheets) and/or to
use the filter aids listed. To an increasing extent, membrane
filtration (cross-flow filtration) is also being used in breweries
in combination with preclarification by separators, for
example.
High-quality beer can be produced with any of these systems. These
types of filtration, such as deadend filtration, sheet filtration
and membrane filtration (cross-flow filtration), which are known in
the state of the art, have various disadvantages.
The main thing to be taken into account in deadend filtration is
the use of filter aids such as diatomaceous earth, to which there
are some health objections, plus the necessity of disposal, as well
as the undesirable input of pro-oxidative metal ions, such as iron,
into the beverage matrix, can be considered as a substantial
disadvantage in comparison with membrane filtration. In addition,
membrane filtration methods are very inflexible with regard to the
available variety of methods and the associated differences in
quality of the filtrate. In deadend filtration, the filtration
performance of the membrane is automatically reduced in the case of
liquids that are more difficult to filter, by adapting the particle
size of the diatomaceous earth mixture to the varying quality of
the unfiltered beer. For this reason, several modules are always
operated in parallel in membrane filter systems, so that, although
a continuous process is possible, it is also associated with a much
higher investment cost. Both operating costs and installation costs
are therefore much higher in membrane filtration in comparison with
deadend filtration; likewise, power consumption and water
consumption are also higher.
Another important disadvantage, which occurs due to the use of
diatomaceous earth, is the unwanted input of heavy metal ions, in
particular the input of pro-oxidative iron or copper. In addition
to the input of iron due to the raw materials (malt, hops, brewing
water, yeast), iron is introduced into beer mainly from the iron
released from the diatomaceous earth precoating, and second, from
the iron released from the continuous diatomaceous earth dosage. A
large portion of the iron is deposited in the first 15 minutes in
deadend filtration at the start of filtration and then declines
continuously. However, continuous dosing of diatomaceous earth
continues to lead to a uniformly high input of iron into the beer.
The total amount of beer-soluble iron and/or the total amount of
copper, although to a lesser extent, depend(s) on the variety of
diatomaceous earth. The recommended limit value is 0.20 mg/L.
However, the latest research findings indicate that much lower
values of <0.05 mg/L are desirable for beer and should be
established as goals because of the strong influence of the metal
ions on the oxidative and colloidal stability of beer.
In the meantime, diatomaceous earth has also been included in the
MAC list (maximum allowed job site levels) and the BAK list by the
"German Research Society (DFG) for Testing Occupational Substances
Hazardous to Health" and should be classified in category 1
"Carcinogenic in humans." Furthermore, disposal of used
diatomaceous earth must also be classified as "special wastes,
monitoring required" and thus makes disposal both complex and
cost-intensive.
Furthermore, attempts to regenerate spent diatomaceous earth that
has become useless as a filter aid have met with only limited
success in practice. Some breweries have switched to the use of
membrane filtration because of the uncertain situation with regard
to additional, more stringent statutory regulations in handling and
disposal of diatomaceous earth as well as advances in technical
developments in recent years in the field of membrane
filtration.
From the aforementioned aspects, the ideal beer filtration would be
deadend filtration without the use of diatomaceous earth, so that
it will be possible to continue using the existing deadend
filtration installations and/or sheet filtration installations in
breweries.
For these reasons, there is an urgent demand for filter aids that
are free of diatomaceous earth.
European Patent EP 1 333 906 B1 describes in this regard
Crosspure.RTM., an alternative regenerable filter aid. This filter
aid consists of 70% polystyrene, which has already been approved
for food production and is already widespread today. Other
ingredients include crosslinked polyvinyl pyrrolidone (PVP) or
polyvinyl polypyrrolidone (PVPP). With these filter aids,
particulate turbidity-causing substances can be removed by a
physical method, and dissolved turbidity-causing polyphenols can be
bound.
However, has been found that the regenerable Crosspure.RTM. filter
aid has a crucial disadvantage because it is prepared from a
mixture of coarse and fine filter aids. After use and subsequent
regeneration, there is also an undefined mixture of coarse and fine
filter aid particles. According to the current state of the art,
this mixture is still unsuitable for practice, i.e., it cannot be
separated in a sufficiently economical manner. Accordingly, there
is no longer adequate precision in the adaptability of the
respective filter aid required in various unfiltered beers and/or
filtration method steps, such as, for example, precoating. The
increased expenses to achieve a sufficient precision once again
results in higher filtration costs than those with comparable
methods.
In addition there have been preliminary attempts, e.g., by F.
Braun, H. Evers, etc. (Frank Braun et al., "Large-Scale Study on
Beer Filtration with Combined Filter Aid Additions to Cellulose
Fibers", Journal of the Institute of Brewing, publication no.
G-2011-0921-1107, 2011) to use untreated cellulose fibers and
silica sol for filtration of beer. In these methods, a second
filtration step is also carried out using a trap filter. However,
this method does not achieve the turbidity values of those in
diatomaceous earth filtration (0.8/0.2 EBC
(90.degree./25.degree.)), which can be used as comparative values
for high-quality beer filtration.
The EBC unit--which is still used below--here stands for European
Brewing Convention, which promotes the scientific activity of
brewing in Europe. EBC units are used to describe, among other
things, the turbidity of beer, the color of beer and the bitter
value of a beer.
The turbidity values which are determined by this method and
expressed in EBC units are determined in accordance with the
MEBAK--Brewing industry analytical methods for beer wort, mixed
beer beverages, a compilation of methods of the Central European
Brewing Industry Analytical Commission, self publication of MEBAK,
D-85358 Freising-Weihenstephan, 2012, ISBN 978-3-9805814-6-2, pages
193-194, point 2.14.1.2.
In the method described by Braun, a horizontal pilot filter is used
for precoating of horizontal layers, and a trap filter with 10
.mu.m columns is used as a secondary filter in a second filtration
step. Due to these two filtration steps, the method according to
Braun is also very complex and therefore cost intensive.
Another disadvantage of the method according to Braun is the
disposal of the cellulose fibers when used in mixture with PVPP or
silica sol and/or silica gel. Thus, the same problems occur here as
when using diatomaceous earth.
Therefore, the object of the present invention is to make available
alternative filter aids for artificial clarification of
turbidity-causing substances from liquids. In addition, the object
of the invention is to provide materials for filter aids, which
overcome the aforementioned disadvantages of the state of the
art.
The present invention therefore provides an alternative filter aid
for replacing diatomaceous earth, which conforms to the qualitative
and economic requirements of brewing science while also permitting
additional benefits in use.
The alternative filter aid is made possible by the method according
to the invention for producing modified cellulose fibers, wherein
the modified fibers eliminate the disadvantages of the state of the
art when used as filter aids in the method for artificial
clarification of turbidity-causing substances from liquids. This
method for producing modified fibers and the modified fibers
themselves are thus the subject matter of the independent claims.
Preferred embodiments are the subject matter of the dependent
claims.
Therefore, one subject matter of the present invention is a method
for producing modified cellulose fibers, comprising one or more of
the following steps:
I. Preparation steps a) Weighing in a fiber mixture consisting of
80-99.9 wt % cellulose fibers, 0.1-10 wt % sodium croscarmellose
and 0-10 wt % of one or more additives;
II. Swelling and preparation steps in a neutral to alkaline range
b) Topping off the initial weight of mixture with a polar solvent;
c) Adjusting the pH;
III. Heating steps d) Heating the initial weight of mixture to the
boiling point while stirring; e) Cooking the initial weight of
substance while stirring; f) Cooling the initial weight of mixture
while stirring;
IV. Washing steps g) Separating the polar solvent; h) Washing the
fibers;
V. Homogenization steps i) Loosening and/or pulverizing by stirring
the moist mass;
VI. Fabrication steps (optionally applicable) j) Drying the moist
mass; k) Isolating and optionally process the modified cellulose
fibers.
The subject matter of the invention is optionally also the modified
cellulose fibers obtained by the method according to the invention,
which can be used as filter aids for artificial clarification of
turbidity-causing substances out of a liquid, consisting of: a)
80-99.9 wt % of a main function substance based on cellulose
fibers; b) 0.1-10 wt % of an auxiliary function substance based on
carboxymethylcelluloses and c) 0-10 wt % of one or more
additives.
In addition, the subject matter of the invention is also a
filtration aid containing one or more cellulose fibers modified
according to the invention.
In a first method step (a), a fiber mixture consisting of 80-99.9
wt % cellulose fibers, 0.1-10 wt % sodium croscarmellose and 0-10
wt % of one or more additives is weighed in for the method
according to the invention.
In particular, fiber mixtures containing, first, cellulose fibers
in the amount of 80-85 wt %, 82-90 wt %, 85-92 wt %, 87-95 wt %,
90-99 wt %, 92-99.0 wt %, 90-99.9 wt %, and, second, containing an
amount of sodium croscarmellose and additional additives are used
and are provided in balancing weight ratios for the method
according to the invention.
The amount of sodium croscarmellose is typically between 0.1 and 3
wt %, 0.1 and 0.5 wt %, 0.2 and 1 wt %, 0.5 and 1.5 wt %, 1 and 3
wt %, 0.8 and 2.5 wt %, 1.2 and 3.5 wt %, 1.5 and 3.8 wt %, 1.8 and
4 wt %; 2 and 4.5 wt %, 2.2 and 4.8 wt %, 2.5 and 6 wt %, 2.5 and 8
wt %, 3.0 and 8 wt %, 3.0 and 6 wt %, 3.2 and 7 wt %, 3.5 and 9 wt
%, 2.5 and 9 wt %, 4.0 and 10 wt %, 4.5 and 10 wt %. For topping
off to 100 wt %, usually one or more additives are provided as
described below.
The total of the ingredients contained in the fiber mixture amounts
to 100 wt % and is comprises of the cellulose fibers, sodium
croscarmellose and/or one or more additives.
The fiber mixture consists of various cellulose fibers of different
lengths and properties. Cellulose fibers are understood to be the
group of fibers including cellulose, cellulose-based fibers, fibers
from grains, from wood, from bamboo, from wood chips, from wood
wastes or mixtures of same. A greater crosslinking between the
individual fibers is achieved due to the inventive and targeted
processing of the cellulose fibers with carboxymethylcelluloses
and/or in particular with sodium croscarmellose, and/or finer
branching is achieved by incorporation of additional compounds.
This is achieved due to the mechanical bonding of the fibers to one
another, on the one hand, and also, on the other hand, due to the
improved chemical binding properties of the modified cellulose
fibers.
The processing of the cellulose fibers according to the invention
imparts to them an additional functionality, which is recognizable
by the improved binding capacity of specific proteins, so that even
turbid-causing proteins and/or protein-polyphenol compounds can be
removed. Subsequently, little to no stabilizer such as silica gel
or diatomaceous earth is needed and the inventive use of the
modified fibers as filter aids is less expensive.
Carboxymethylcelluloses (CMC) are cellulose ethers, i.e.,
derivatives of cellulose in which some of the hydroxy groups are
linked as ethers to a carboxymethyl group (--CH.sub.2--COOH). For
production, the celluloses obtained from coniferous and deciduous
woods or cellulose are ground and converted to the more reactive
alkali cellulose with sodium hydroxide solution. Alkylation of the
alkali cellulose to carboxymethylcellulose is carried out in
chloroacetic acid. The cellulose structure is retained and the acid
form is insoluble in water. However, carboxymethyl celluloses are
readily soluble in basic solutions.
In the EU, carboxymethylcellulose is approved as a food additive
with the number E 466. In this regard, disposal of the filter aid
according to the invention consisting of the modified cellulose
fibers containing CMC is less cost-intensive and instead this
filter aid can be composted in the simplest possible manner.
Furthermore, approval as an animal feed or feed additive is also
possible. Sodium croscarmellose is a water-insoluble variant of
carboxymethylcellulose produced by crosslinking.
It is known in general that sodium croscarmellose is a swellable
water-insoluble polysugar that is used as an additive in
pharmaceutical production and in food technology. Crosslinking of
the carboxymethyl cellulose polymer chains takes place by means of
glycolic acid which is formed there from excess chloroacetic acid
from the previous method step in carboxymethylcellulose.
Deprotonation of the carboxyl groups by the acid that is formed
then makes it possible for bonds to other polymer chains to be
formed. The degree of crosslinking can be controlled through the pH
and the temperature. No crosslinking agents are used there. Due to
the crosslinking of the polymer chains, sodium croscarmellose is
practically insoluble in water, but it has a high water-binding
capacity and swells to four to eight times its original volume by
absorbing water. The swelling of the fibers and the enlarged volume
as a result advantageously yield an improved uptake behavior
(filtration behavior) for turbidity substances. Sodium
croscarmellose is virtually insoluble in acetone, ethanol, toluene
and diethyl ether. In addition, it is interesting that sodium
croscarmellose is not absorbed by the human body.
Additives for use in the method according to the invention include
excipients and/or additives, which can be added to the fiber
mixture to achieve a positive effect on the production and/or
storage and/or processing and/or properties of the modified
cellulose fibers during or after filtration. The additives that are
used meet the requirements of good environmental compatibility, low
health risk, high economy and high stability. Preferred additives
for the method according to the invention include, for example, one
or more of the additives selected from the group of additives
consisting of pectin, carrageenan, isinglass, hydrocolloids,
starch, gallotannins, silica sol, silica gel, polyvinylpyrrolidone,
polyvinylpolypyrrolidone (PVPP), which may be added alone or in
mixtures. These additives improve the technical usability and
further increase the filter performance of the modified cellulose
fibers.
In method step (b) of the method according to the invention, the
initial weight of the mixture from method step (a) is topped off
with a polar solvent. Examples of polar solvents include solvents
from the group of solvents containing water, alcohol, aqueous
solutions with carboxylic acids, amines or mixtures of same.
In method step (c), the pH is adjusted for processing the cellulose
fibers. In workup of the fibers, the adjustment of pH is a step
that alters the reaction process. The method according to the
invention is preferably carried out in an alkaline or weakly
alkaline to neutral pH range or even in a weakly acidic range. It
has been demonstrated that the method according to the invention
can be carried out in a pH range from pH 6 to pH 13.
Depending on the starting materials used, it is advantageous to
adjust the pH and to ascertain the pH at which unwanted
constituents such as metal ions are washed out. Since other
ingredients are to be expected for different starting materials, it
is possible according to the present invention to adjust the pH
with one or more acids or bases. Those skilled in the art usually
use HCl or NaOH for this purpose.
In experiments at various pH levels, it has been found that a
significant increase in the iron level in the polar solvent can be
measured by adjusting the pH in the alkaline range at pH.gtoreq.9
and by using a few starting materials. This iron level is partially
washed out as iron oxide that is formed in workup of the fibers and
can thus no longer enter the beer subsequently during the
filtration process (Table 1).
TABLE-US-00001 TABLE 1 Iron measurement in section filtered workup
solution Croscarmellose pH in Standard sodium workup Iron deviation
Fiber % -- ppb ppb Cellulose 2 -- 125 2.2 fiber A Cellulose 2.5 --
207 0.0 fiber A Cellulose 3 9 442 5.7 fiber A
It should thus be emphasized in particular that carrying out the
method in the alkaline range brings additional advantages for
application of the modified fibers according to the invention in
filtration.
Workup is carried out while stirring in method steps (d) through
(f). The stirring may be performed by a magnetic stirrer, for
example, but this does not preclude the use of other methods for
stirring the initial weight of the mixture, nor is it limited to
these methods.
The initial weight of the mixture is cooked while stirring in
method steps (d) and (e). The cooking operation may take up to 360
minutes. The cooking process may also last longer than 360 minutes,
depending on the fiber used and/or previous and/or subsequent
processes.
Modified cellulose fibers that lead to a reduction in turbidity in
the filtration process and to a reduction in the turbidity value
from 45 EBC to 19 EBC can be obtained even after a 60-minute
cooking process. Therefore, workup of the cellulose fibers leads to
a significant improvement in turbidity values in the downstream
filtration processes.
Cooking is preferably maintained at a cooking temperature in the
range between 60.degree. C. and 105.degree. C., alternatively,
60.degree. C. to 80.degree. C., 70.degree. C. to 90.degree. C.,
80.degree. C. to 105.degree. C. Cooking may also take place under
pressure, so that cooking temperatures above the boiling point of
the respective polar solvent can be achieved. Cooking at a slight
excess pressure is provided in industrial production.
In method step (f), the fiber mixture is cooled while stirring.
In method step (g) the polar solvent is separated from the initial
rate of the mixture by suction filtration by means of a vacuum pump
through filter paper, for example. Separation of the polar solvent
is not limited to the vacuum pump here. Additional methods known in
the prior art can also be used here for suction filtration and/or
separation.
In method step (h), for example, the initial weight of mixture is
washed with double-distilled water, tap water, slightly alkaline or
slightly acidic solution, saline solution (e.g., NaCl solution) by
renewed suction filtration and/or separation using a vacuum
pump.
In method step (i), the moist mass is loosened by stirring,
pulverized and/or homogenized. Other loosening, pulverizing or
homogenizing methods with which those skilled in the art are
familiar may also be used.
In optional method step (j), the moist mass is dried to a residual
water content of approx. 2% to 10%. The modified cellulose fibers
are made more stable and transportable by this drying and can be
used in an automatic application for filtration after this
processing step. However, the modified cellulose fiber can also be
used directly in the filtration method, e.g., for deadend
filtration even without method step (j) using the present moist
mass. For example, drying is advantageous if the modified cellulose
fiber is then pressed to form sheets for use in a sheet filter, for
example.
In method step (k) the modified fiber is isolated. Isolation may
also be understood to mean that the modified cellulose fiber is
converted from the modification process only in the filtration
process.
The method steps (b) and (d)-(k) can of course be combined,
exchanged, replaced and modified freely within the scope of the
known prior art.
The term "modified cellulose fiber" is understood to refer to a
thermal and/or mechanical and/or chemical action and/or cellulose
fibers with which the filtration properties are improved that have
been modified in a targeted manner by additives.
For example the iron content in the fibers can be reduced
significantly through the inventive workup of the cellulose fibers
and therefore the filtration related iron input which has an
oxidative action is reduced significantly in comparison with the
use of diatomaceous earth as a filter aid. Subsequently a greater
oxidative stability of beer can be achieved. In addition the
cellulose fiber that has been worked up according to the invention
allows an additional binding of turbidity-causing proteins and/or
protein polyphenol compounds and a greater colloidal stability of
beer can be achieved through this additive effect in comparison
with filtration using diatomaceous earth or crude cellulose
fibers.
Therefore the addition of the stabilizers that are generally used
such as PVPP or silica sol or silica gel can be reduced while
achieving the same colloidal stability so that the filtration can
be carried out less expensively.
The cellulose fibers are selected from the group of fibers
consisting of cellulose, cellulose-based fibers, fibers made of
grains, wood, bamboo, wood chips, wood wastes or mixtures of same.
These fibers have an average fiber length in the range of <1 to
500 .mu.m. The phrase "fibers with an average length" is understood
to refer to the production-related scattering and the phrase
"combined use of fibers with different lengths" is understood to
refer to an average range of 1-500 .mu.m. The fibers may have
different fiber lengths (long fibers, short fibers), because the
dead head behavior is influenced to a great extent on the average
fiber length and the specific gravity or fineness of the cellulose
fibers. The use of cellulose fibers to produce modified cellulose
fibers yields additional advantages for the use of these fibers for
a filter aid: Despite the high cost of acquisition of cellulose
fibers in comparison with diatomaceous earth filtration, the
profitability aspect is improved. Lower operating costs can be
implemented due to the lower mass demand with the same filtration
capacity.
The cellulose that is used as the starting material for production
of fibers for filtration is a renewable raw material. The
diatomaceous earth that can be mined above ground originates from
the crushed fossilized shells of silaceous algae (diatoms)
approximately 15 million years ago, and therefore the quantity is
limited. In this regard, a price increase is highly likely in the
future because of the shortage of this resource and therefore
access to renewable raw materials must be considered to be highly
advantageous.
As already mentioned above, diatomaceous earth has already been
included in the MAC and BAK lists because of the problem of dust
production and is classified in category 1 "Carcinogenic in
humans."
For filtration of beer, there has been an increased search for
suitable alternatives to diatomaceous earth filtration in this
regard. Filtration using a filter aid based on cellulose fibers is
a process which suppresses excessive dust production.
In comparison with filtration with diatomaceous earth, no iron ions
or at least definitely fewer iron ions are introduced into beer
when using a filter aid according to the invention. Therefore,
fewer radicals are formed, so that the endogenous antioxidative
potential of the beer is reduced to a much lesser extent and
therefore its oxidative stability is improved. Subsequently, the
result is a more stable taste and furthermore the colloidal
stability is prolonged.
In the prior art, beer is treated with stabilizers such as PVPP or
silica gel to improve the physical stability of the beer. This
removes the turbidity-causing polyphenols (PVPP) polyvinyl
polypyrrolidone or proteins (silica gel), i.e., polyphenol-protein
compounds during the brewing process to obtain a greater turbidity
stability in ready-to-sell beers. This step typically takes place
in both deadend filtration as well as membrane filtration.
Due to the inventive modification of the cellulose fibers, the
fibers have an additional functionality so that turbidity-causing
proteins and/or protein-tannin compounds can be removed by
filtration. Therefore this creates an increase in value, which
substantially improves not only the investment cost but also the
operating cost of a brewery due to the reduction in the use of
and/or complete avoidance of additional stabilizers.
In one embodiment of the invention, the fiber mixture according to
method step (a) consists of 92-99 wt % cellulose fibers, 1-8 wt %
sodium croscarmellose and 0.4 wt % of one or more additives.
In another embodiment of the invention, the fiber mixture according
to method step (a) is selected from a composition consisting of
90-99.9 wt % cellulose fibers, 0.1-5 wt % sodium croscarmellose and
0-5 wt % of one or more additives or 90-99 wt % cellulose fibers
and 1-5 wt % sodium croscarmellose and 0-5 wt % of one or more
additives. A composition containing 96 wt % cellulose fibers, 3 wt
% sodium croscarmellose and 1 wt % additives is especially
preferred.
According to additional embodiments, the additives are selected
from the group consisting of pectins, carrageenans, isinglass,
hydrocolloids, starch, gallotannins, silica sol, silica gel,
polyvinyl pyrrolidones and/or polyvinylpolypyrrolidone (PVPP). Due
to the use of additives, in particular pectins, carrageenan,
isinglass, hydrocolloids, starch, the industrial usability can be
improved and the filtration efficacy can also be increased. Thus, a
further improvement in the modified cellulose fibers and in
particular an improved filtration of protein constituents or metal
ions, for example, can be achieved.
The pH according to method step (d) is adjusted with at least one
acid, preferably hydrochloric acid (HCl), and/or with at least one
base, preferably sodium hydroxide (NaOH), to a pH of pH 6-pH 13,
alternatively to pH 7-pH 12, pH 8-pH 11, pH 8-pH 12, pH 9-pH 11, pH
7-pH 10, pH 11-pH 12, further alternatively with sodium hydroxide
to a pH>9 or with sodium hydroxide to a pH between pH 11-pH
13.
To lower the pH, acids from the group of acids containing
hydrochloric or phosphoric acid or mineral acids such as sulfuric
acid and nitric acid or sulfurous acid may be used. To increase the
pH, bases from the group of bases containing sodium hydroxide,
ammonia, lime water, amines may be used.
The cellulose fibers as the main function ingredient are selected
from the group of fibers containing cellulose, cellulose-based
fibers, fibers made of grains, wood, bamboo, wood chips, wood
wastes or mixture of same, and wherein the fibers have an average
fiber length in the range of <1 .mu.m to 500 .mu.m.
As an additive function substance, 0.1-10 wt % sodium
croscarmellose is present as a water-insoluble variant of
carboxymethylcellulose.
Additives from the group of pectins, carrageenans, isinglass,
hydrocolloids, starch, gallotannins, silica sol, silica gel,
polyvinylpyrrolidone and/or polyvinylpolypyrrolidone are used as
the additives.
When using the modified or optionally dried or isolated cellulose
fibers for artificial clarification, the modified cellulose fibers
have a pH in the range of pH 5 to pH 8 when the cellulose fibers
that have been modified according to the invention are dissolved or
swollen again in water.
In addition, the invention provides a filter aid which contains one
or more cellulose fibers modified according to the invention. This
filter aid can be produced as a deadend tubular filter, for
example, or as a deadend sheet filter. To do so, the fibers that
have been modified according to the invention and optionally dried
are layered, tamped, absorbed, pressed or poured in accordance with
the technical requirements.
The filter aid is preferably used in a method for artificial
clarification of turbidity-causing substances from a liquid with a
precoating of the filter aid in a first step, for filtration of the
liquid to be clarified through the filter aid in a second step and
for use of the filter aid as a running dosage during filtration in
a third step.
The method is not limited to the steps listed here and instead
additional steps and/or intermediate steps may also be carried out.
The use of a filter aid is also not limited to a single filter aid
and/or the steps listed. Instead, various filter aids of different
mixtures and percentage amounts by weight of the main function
ingredients and/or auxiliary function substances and/or one or more
additives may be used.
Deadend filtration is described here as an example of a method for
artificial clarification. In deadend filtration, for example, a
deadend tubular filter is used. In addition, a deadend sheet filter
and/or a sheet filter may be used.
Various experiments in adjusting the method according to the
invention and producing the modified cellulose fibers as well as
the results thereby achieved are explained in greater detail below,
wherein these experiments explain the invention only as an example
on the basis of laboratory experiments and experiments in the
research brewery of TU Berlin and do not constitute a restriction
on the general idea of the invention with respect to
modifications.
In the figures:
FIG. 1 shows the filtration curve of the Filtrox filtration
experiments with diatomaceous earth;
FIG. 2 shows the filtration curve of the Filtrox filtration
experiments with crude fiber/modified cellulose fiber A;
FIG. 3 shows the turbidity curve over the entire filtration
experiment with crude fiber/modified cellulose fiber A;
FIG. 4 shows the behavior of modified cellulose fibers with various
amounts of sodium croscarmellose;
FIG. 5 shows the experiments with different pH levels in the workup
of the modified fibers with 2 wt % sodium croscarmellose;
FIG. 6 shows the filtration curve of the experiment with sodium
croscarmellose-modified cellulose fiber A;
FIG. 7 shows the turbidity curve of the entire filtration time when
using the modified cellulose fiber A;
FIG. 8 shows the filtration curve with diatomaceous earth;
FIG. 9 shows the turbidity curve with diatomaceous earth;
FIG. 10 shows the filtration curve with crude fiber/modified
cellulose fiber A;
FIG. 11 shows the turbidity curve with crude fiber/modified
cellulose fiber A;
FIG. 12 shows the filtration curve with modified cellulose fiber A
with 3 wt % sodium croscarmellose at pH 11;
FIG. 13 shows the turbidity curve with modified cellulose fiber A
with 3 wt % sodium croscarmellose at pH 11;
FIG. 14 shows the filtration curve with modified cellulose fibers A
and B with 3 wt % sodium croscarmellose at pH 11;
FIG. 15 shows the turbidity curve with modified cellulose fibers A
and B with 3 wt % sodium croscarmellose at pH 11; and
FIG. 16 shows the ESR measurement of beers from additional
experiments.
EXAMPLES
To better evaluate the suitability of the modified cellulose
fibers, beer filtration experiments were conducted with the
cellulose fibers (fiber A and fiber B).
Before that, the comparative filtration and/or reference filtration
was carried out using the filter aid diatomaceous earth on the
Filtrox system. There were two precoatings (VA) and filtration
(Table 2).
Immediately after the start of filtration, a significant increase
in the differential pressure can be discerned (FIG. 1). However,
the filtration was not carried out at a constant flow rate but
instead at the flow rate that was automatically adjusted, depending
on the resistance. The filter tube was completely closed after the
first coating and the turbidity values were in a very good range
for the pilot filter plant with 0.9/0.3 EBC 90.degree.
C./25.degree. C.
TABLE-US-00002 TABLE 2 Two precoatings Filtration Diatomaceous
earth type 20 min first runnings 3500: 82 g (37.3 kg)
(corresponding to 600 g/m.sup.3) Running dosage: 100 g/hL in 3
liters of diatomaceous earth water type 1200 and Diatomaceous earth
type diatomaceous earth type 1200 and diatomaceous 200 (2:1) earth
type 200: 82 g Three filtrate drums - (2:1) in 3 liters of
beginning, middle, end water Circulating pump: 10%, throttled to
4.0 L/min (17.6 hL/m.sup.2h) Dosage pump: frequency 100%, vol. 25%
Dosage duration: 27 min Circulation: approx. 10 min
In comparison with the diatomaceous earth reference filtration, a
cellulose fiber filtration was always carried out on the same
Filtrox system using a dosage adapted to the modified cellulose
and/or cellulose-based fibers.
For the cellulose fiber filtration, a precoating and the filtration
were carried out (Table 3). FIG. 2 illustrates the atypical
filtration curve of filtration with a crude fiber. As soon as the
filter was filled with beer, the 25.degree. C. value was outside of
the turbidity measurement range (>2.1 EBC) (FIG. 3). The
filtration performance of the cellulose-based fiber (crude fiber) A
was not adequate for filtration of beer at 20.degree. C. because of
turbidity values of 1.4/1.8 EBC 90.degree. C./25.degree. C. At
0.degree. C., the values are in the turbidity range (>2 EBC)
with 3.5/2.5 EBC 90.degree. C./25.degree. C.
TABLE-US-00003 TABLE 3 Precoatings Filtration 1000 g fiber/m.sup.2
in 5 13 kg first runnings liters of water Running dosage: 60 g
Circulating pump: 10%, fiber/hL throttled to 11.5-12 L/min Two
filtrate drums of Dosage pump: frequency 30 L - beginning, end
100%, vol. 40% Dosage duration: approx. 40 min Circulation: approx.
20 min
As a result it can be concluded that Filtration aids and/or crude
fibers based on unaltered cellulose can be used in conventional
plant technologies for filtration; Cellulose-based filter aids can
be considered to be a permanent filter aid because it is produced
from renewable raw materials; Disposal of cellulose-based
fibers/filter aids after filtration can be classified as
unproblematical.
The cellulose-based crude fibers and/or corresponding filter aids
that are used exhibit good properties of a filter aid in coating in
general (rapid circulation and thus rapid throughput time,
homogeneous distribution and thus low filter resistance) but they
do not have an adequate filtration performance, i.e., despite the
relatively great layer thicknesses, the beer is not filtered or is
not filtered until clear in accordance with the claim when using
the forms and cut sizes used so far. Because of the high turbidity
values, the crude fibers based on untreated cellulose with >40
EBC (90.degree. C.) and >15 EBC (25.degree. C.) must be
classified as unsuitable for filtration of beer.
Various amounts (0, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5%) sodium
croscarmellose were used for workup of the cellulose-based crude
fibers according to the invention, and the altered filter
properties were checked by using a Stabifix Filter Check apparatus.
Crude cellulose fiber A was therefore modified with sodium
croscarmellose according to the method according to the invention.
FIG. 4 shows the data determined in the lab filter test using the
Stabifix Filter Check apparatus.
The Stabifix Filter Check apparatus measurement method is based on
the MEBAK--Industrial Brewing Analytical Methods for Wort, Beer,
Mixed Beer Beverages, Compilation of Methods of the Central
European Industrial Brewing Analysis Commission, self publishers of
the MEBAK, D-85350 Freising-Weihenstephan, 2012, ISBN
978-3-9805814-6-2, pages 271-273, point 2.20.2, and the method was
modified in this regard to conform to additional requirements.
The use of 0.5 wt % sodium croscarmellose for workup resulted in an
improvement in the turbidity values only to a limited extent, but
significantly improved turbidity values were obtained in the ranges
of Stabifix (laboratory-scale) diatomaceous earth filtration with
values of 3.4 EBC (90.degree. C.) and/or 0.8 EBC (25.degree.
C.).
Up to the amount of approx. 2.5% sodium croscarmellose for workup,
there is a further significant improvement in the filtration
properties. At higher amounts of sodium croscarmellose, the
turbidity appears to lie in a linear region.
In another preliminary experiment, the influence of the pH on
workup was ascertained (Table 4). The cellulose fiber A was
modified by the method according to the invention with sodium
croscarmellose with a pH adjusted in the range of pH 3 to pH 5,
with no change in pH and/or in a pH range from pH 9 to pH 11 by the
method according to the invention. A significant improvement in
filtration performance was achieved only beyond a pH in the neutral
to alkaline range. FIG. 5 shows the results with 2 wt % sodium
croscarmellose in the pH range of pH 3 to pH 11.5. Another definite
improvement in filtration properties can be seen in the pH range
>9.
TABLE-US-00004 TABLE 4 Turbidity values after filtration using
cellulose fiber A processed with sodium croscarmellose Sodium
croscarmellose Turbidity Standard Turbidity Standard addition pH
90.degree. deviation 25.degree. C. deviation Fiber % -- EBC EBC EBC
EBC Diatomaceous -- -- 2.3 0.2 0.7 0.1 earth Cellulose -- -- 45.3
1.5 18.1 1.7 fiber A Cellulose 2 3.5 4.0 0.01 2.34 0.12 fiber A
Cellulose 2 5.5 2.6 0.05 1.3 0.03 fiber A Cellulose 2 5.7 3.2 0.03
1.6 0.11 fiber A Cellulose 2 9.8 2.4 0.19 1.1 0.24 fiber A
Cellulose 2 11.3 1.7 0.01 0.7 0.01 fiber A Cellulose 3 9.3 2.2 0.06
0.7 0.03 fiber A Cellulose 3 11.1 1.5 0.01 0.6 0.04 fiber A
In a subsequent experiment with the Filtrox installation, a
cellulose fiber based on fiber A modified by the method according
to the invention and containing an amount of 2 wt % sodium
croscarmellose was worked up. In comparison with the diatomaceous
earth reference filtration, filtration with the modified cellulose
fibers was carried out on the same Filtrox installation using a
dosage adapted to the cellulose-based crude fiber. For fiber
filtration with the modified cellulose fiber, a precoating and
filtration were carried out (Table 5).
TABLE-US-00005 TABLE 5 Precoatings Filtration 1000 g fiber/m.sup.2
in 5 13 kg first runnings, liters of water then 5 minutes
Circulating pump: 10%, circulation throttled to 11.5-12 L/min
Running dosage: 60 g Dosage pump: frequency modified fiber/hL 100%,
vol. 40% Two filtrate drums of Dosage duration: approx. 30 L -
beginning, end 40 min Height of layer for Circulation: approx. 20
min precoating Height of layer at end of filtration 12.5 .+-. 0.3
mm Turbidity EBC 90.degree. C./25.degree. C.; 0.9/0.4
The filtration experiment with sodium croscarmellose-modified
cellulose-based on fiber A shows a typical filtration curve (FIG.
6) in contrast with the curve for diatomaceous earth filtration
(FIG. 1), but it is comparable to the curve for crude fiber A
filtration (FIG. 2). The atypical filtration curve thereby
established is manifested in the differential pressure that is very
low or even barely measurable during filtration. It can be
concluded from this that a portion of the filtration effect is
therefore based on absorption. In diatomaceous earth filtration,
the differential pressure is the most important influencing factor,
but here again, there is only minor absorption.
The minor differential pressure when using sodium
croscarmellose-modified cellulose fiber is very advantageous
because this makes it possible to carry out filtration for a longer
period of time and therefore to filter a greater volume. In the
case of diatomaceous earth filtration, the filtration must be
terminated at an admissible maximum pressure of 5-6 bar because of
the steady increase in the differential pressure during filtration.
This results from the steady increase in the filter layer because
of the ongoing diatomaceous earth dosage, which ensures a uniform
filtration performance with a rising input pressure. In filtration
with sodium croscarmellose-modified cellulose fibers, filtration,
which is definitely longer and therefore more economical, is
possible due to the low and/or hardly measurable increase in the
differential pressure. The turbidity values (FIG. 7) are much lower
in comparison with those obtained by filtration using crude
cellulose fibers (FIG. 3), and are all within the measurement range
(<2.1 EBC). The turbidity measurements in the laboratory at
20.degree. C. are also definitely in the range for a clear beer
with 0.9/0.4 EBC (90.degree./25.degree.). Furthermore, these values
are in the same range as the values for diatomaceous earth
filtration in the same Filtrox pilot plant (0.9/0.4 EBC
90.degree./25.degree.). Even at 0.degree. C. good turbidity values
of 1.1/0.5 EBC (90.degree./25.degree.) have been measured due to
the use of the modified cellulose-based fibers; these turbidity
values are in the invisible range. Therefore, a significant
reduction to 1/3 of the turbidity value in comparison with that of
the unprocessed cellulose-based fiber can be achieved.
It should be pointed out in particular that sodium croscarmellose
and/or the modified cellulose-based fibers can bind proteins.
Between the running dosage and achieving the filter cake,
precipitation and/or flocculation can easily occur in a beer. Such
precipitation and/or flocculation is bound by the cellulose fibers
modified with sodium croscarmellose. Thus, a protein-side
stabilization of turbidity can be achieved by filtration using
cellulose fibers modified by the method according to the
invention.
The results of the beer analysis of the unfiltered substance (beer)
as well as filtered beer from experiments with 2 wt % sodium
croscarmellose and crude cellulose fiber A are compared in Table
6.
TABLE-US-00006 TABLE 6 Result of standard beer analysis 2% NCM 2%
NCM Cellulose cellulose cellulose Cellulose fiber A fiber A fiber A
fiber A Unfiltered 1 beginning end beginning end Original .degree.P
12.1 11.5 11.7 11.5 11.5 wort Extract, % 2.12 2.06 2.10 2.06 2.10
apparent w/w Extract, % 4.04 3.89 3.95 3.88 3.95 actual w/w Alcohol
% 5.31 5.02 5.09 5.01 5.09 v/v Color EBC 6.6 6.4 6.5 6.1 6.3 pH --
4.42 4.41 4.40 4.41 4.40 Turbidity, EBC >100 3.46 3.4 1.12 1.14
0.degree. C. 90.degree. Turbidity, EBC >100 2.45 2.26 0.53 0.53
0.degree. C. 25.degree. Turbidity, EBC >100 1.37 1.19 0.90 0.88
20.degree. C. 90.degree. Turbidity, EBC >100 1.42 1.09 0.43 0.38
20.degree. C. 25.degree.
In an additional experiment using a Filtrox plant, a cellulose
fiber A modified by the method according to the invention was
worked up with 3 wt % sodium croscarmellose, and a modified
cellulose fiber B was worked up with an amount of 3 wt % sodium
croscarmellose. In comparison with the diatomaceous earth reference
filtration (Table 7), filtration with the modified cellulose fibers
was carried out using the same Filtrox pilot plant with a dosage
adapted to the modified crude cellulose fiber (Table 8). For
cellulose fiber filtration (fiber A), precoating and filtration
were carried out; a first and second precoating and filtration with
an ongoing dosage were carried out for the combination A+B
(modified cellulose fiber A and B, each containing 3 wt % sodium
croscarmellose at pH 11) (Table 9).
TABLE-US-00007 TABLE 7 Two precoatings Filtration Diatomaceous
earth type 20 min first runnings 3500: 82 g (37.3 kg)
(corresponding to 600 g/m.sup.2) Running dosage: 100 g/hL in 3
liters of diatomaceous earth water type 1200 and Diatomaceous earth
type diatomaceous earth type 1200 and diatomaceous 200 (2:1) earth
type 200: 82 g Three filtrate drums - (1:1) in 3 liters of
beginning, end water Circulating pump: 10%, throttled to 4.0 L/min
(17.6 hL/m.sup.2h) Dosage pump: frequency 100%, vol. 25% Dosage
duration: 27 min Circulation: approx. 10 min
TABLE-US-00008 TABLE 8 Precoatings Filtration 1000 g/m.sup.2
modified fiber 13 kg first runnings, in 5 liters of water then 5
minutes Circulating pump: 10%, circulation throttled to 11.5-12
L/min Running dosage: 60 g Dosage pump: frequency modified fiber/hL
100%, vol. 40% Two filtrate drums of Dosage duration: approx. 30
liters each - 40 min beginning, end Circulation: approx. 20 min
TABLE-US-00009 TABLE 9 Two precoatings Filtration 500 g/m.sup.2
modified fiber 13 kg first runnings, in 5 liters of water then 5
minutes Circulating pump: 10%, circulation throttled to 11.5-12
L/min Running dosage: 60 g Dosage pump: frequency modified fiber/hL
100%, vol. 40% Two filtrate drums of Dosage duration: approx. 30
liters each - 40 min beginning, end Circulation: approx. 20 min
Definite advantages of filtration using modified cellulose fibers
can be seen from the key data in the figures shown. Thus, FIG. 8
shows the filtration curve of a normal diatomaceous earth
filtration. As is customary in diatomaceous earth filtration, the
differential pressure increases almost linearly. The turbidity
values from the inline measurement (FIG. 9) are not directly in the
range of a diatomaceous earth filtration, as is customary
industrially, where the measured values are always somewhat
elevated in the pilot plant.
In crude fiber filtration (cellulose fiber A) a highly atypical
filtration curve is again obtained (FIG. 10) and there is no
measurable pressure difference. The turbidity values are very high
and are permanently outside of the measurement range (FIG. 11).
A similarly atypical filtration curve in filtration with modified
cellulose fiber A (modified with 3% sodium croscarmellose at pH 11)
can be seen, like that with crude fiber A (FIG. 12). The turbidity
values (FIG. 13) can be measured inline over the entire filtration
period and increase only slightly over the filtration time. The
experiment with two precoatings (cellulose fiber A with 3% sodium
croscarmellose, pH 11 and cellulose fiber B with 3% sodium
croscarmellose pH 11) also shows almost no pressure different (max.
0.2 bar) over the filtration curve (FIG. 14). Here there is a
stronger linear increase in turbidity (FIG. 15) during
filtration.
Table 10 shows the results obtained by beer analysis of the
unfiltered beer as well as the filtered beers from the experiments
with diatomaceous earth, crude cellulose fiber A, cellulose fiber A
with 3 wt % sodium croscarmellose and pH 11 and cellulose fiber
A/cellulose fiber B, each with 3 wt % sodium croscarmellose and pH
11. The original wort contents show a slight dilution effect in
comparison with the unfiltered beer, which is due to the technical
aspects of the process. However this dilution is comparable in all
the experiments that were conducted, which is also reflected in the
extra values and in the individual alcohol content. In the case of
diatomaceous earth as well as the modified cellulose fiber
filtration, the color values reveal a natural decline due to the
filtration process. The pH is comparable in all beers and a slight
decline in SO.sub.2 can be explained by the minor dilution effect
as well as a small amount of oxygen input during filtration. The
polyphenol contents are significantly lower in comparison with the
diatomaceous earth when using the modified cellulose fiber A. This
has a positive effect on the colloidal beer stability, the tendency
to turbidity during storage/aging is reduced. A greater discharge
due to the modified cellulose fibers can also be detected with the
free amino nitrogens in comparison with diatomaceous earth. The
turbidity values do not yet correspond on the whole to the
guideline values for a clear beer, but again there is a significant
improvement when using modified cellulose fiber (diatomaceous earth
2.2/2.5 EBC (90.degree./25.degree.), crude cellulose fiber 3.1/3.9
EBC (90.degree./25.degree.) and modified cellulose fiber A 1.5/1.3
EBC (90.degree./25.degree.)). The turbidity values obtained for
filtration using modified cellulose fibers are below the reference
diatomaceous earth filtration on the same pilot plant. In other
words, by using modified cellulose fibers in comparison with
diatomaceous earth, the resulting beer has at least a comparable
clarity. A further improvement can be expected by a further
adaptation of the process here. In combined use of modified
cellulose fiber A and modified cellulose fiber B, another
significant increase in the filtration performance (lower turbidity
values 1.0/0.8 EBC (90.degree./25.degree.)) can be detected at the
beginning of filtration. At cold temperatures (0.degree. C.),
values at least equal to those obtained in diatomaceous earth
filtration are achieved by using modified cellulose fibers. An
adaptation in the filtration parameters (amount of coating, running
dosage, amount of croscarmellose, fiber geometry) is possible when
using modified cellulose fibers, depending on the quality of the
unfiltered beer, so that even beer that is difficult to filter can
be filtered to yield a clear product without an increase in the
pressure difference.
FIG. 16 shows the ESR measurement (electron spin resonance
measurement) of beers for investigating the filtration influences
on the oxidative stability of beer. The results of the EAP
determination (endogenous antioxidative potential) illustrate the
basic advantage of a cellulose fiber filtration in comparison with
diatomaceous earth filtration because significantly less iron is
introduced into the beer in comparison with diatomaceous earth.
Therefore, the oxygen activation is reduced by iron ions and fewer
radical are formed by the Fenton reaction system. Subsequently the
filtration-induced loss of endogenous antioxidative potential of
beer is reduced and the taste stability over storage time is
prolonged. This is true in particular of the sodium
croscarmellose-modified cellulose fibers. When using crude
cellulose fibers, a T.sub.600 value can be achieved with approx.
half the ESR signal intensity of diatomaceous earth and generation
of radicals is greatly reduced accordingly. Furthermore, there is a
discernible difference between the beginning and end of the crude
fiber filtration because during the filtration process the iron is
washed out of the filter cake (Table 10) when using modified
cellulose fibers with sodium croscarmellose, the ESR signal
intensity is almost ideally at the level of the unfiltered beer, so
that the negative effect of diatomaceous earth filtration can be
prevented almost completely. The explanation is given by the fact
that a large amount of the iron is already removed from the
cellulose fibers due to the workup of the cellulose fiber A
according to the invention, and therefore iron can no longer enter
the beer. The slightly elevated ESR value can be explained by a low
level of oxygen input during filtration.
When using processed cellulose fiber B, there is a greater input of
iron into beer due to technical conditions because of the lower
discharge of iron in fiber processing. This becomes significant as
soon as the capacity of the underlying filter cake of modified
cellulose fiber A is exhausted. This is when the turbidity also
increases. Regardless of that, it is possible, by adapting the
processing according to the invention, to further minimize the
input of iron even with the modified cellulose fiber B.
The EAP determination by electron spin resonance spectroscopy was
carried out in accordance with the MEBAK Industrial Brewing
Analytical Methods for Beer Wort and Mixed Beer Beverages,
Compilation of Methods of the Central European Industrial Brewing
Analysis Commission, self publication of the MEBAK, D-85350
Freising-Weihenstephan, 2012, ISBN 978-3-9805814-6-2, pages
207-218, point 2.15.3.
TABLE-US-00010 TABLE 10 Result of a standard beer analysis 3% NCM
pH 11 3% NCM 3% NCM cellulose pH 11 pH 11 3% NCM fiber A +
cellulose Diatomaceous Diatomaceous Cellulose Cellulose cellulose
pH 11 cellulose fiber A + Unfiltered earth earth fiber A fiber
fiber A cellulose fiber B cellulose beer 3 beginning end beginning
A end beginning fiber A end beginning fiber B end Original
.degree.P 11.81 11.08 11.31 11.43 11.60 11.19 11.45 11.36 11.56
wort Extract % 1.99 1.90 1.95 1.96 1.99 1.91 1.95 1.92 1.95 w/w
Extract % 3.88 3.67 3.75 3.8 3.84 3.69 3.78 3.73 3.79 w/w Alcohol %
5.21 4.85 4.96 5.02 5.09 4.91 5.03 5.00 5.09 v/v Color EBC 8.2 6.6
6.7 8.2 8.0 6.5 6.8 pH -- 4.38 4.38 4.38 4.38 4.40 4.38 4.41 4.45
Bitter unit EBU 31.2 32.2 32.0 34.3 34.1 34.3 33.3 34.2 Polyphenols
mg/L 207.8 204.3 209.4 213.8 191.1 197.3 SO.sub.2 mg/L 7.1 6.5 6.7
5.5 6.2 6.0 6.4 5.7 5.9 Iron .mu.g/L 14.5 43.4 32.2 28.2 17.1 14.0
11.5 11.7 28.1 FAN mg/L 106.1 100.4 100.0 99.7 103.9 97.0 98.7
Turbidity, EBC >100 2.2 1.9 1.1 8.1 2.1 2.2 1.4 3.7 0.degree. C.
Turbidity, EBC >100 2.9 2.0 13.8 10.8 1.9 1.9 1.1 2.2 0.degree.
C. Turbidity, EBC >100 2.2 1.6 4.1 3.1 1.5 1.5 1.0 2.6
20.degree. C. Turbidity, EBC >100 2.5 1.6 5.1 3.9 1.3 1.3 0.8
1.4 20.degree. C.
* * * * *